DE2630568A1 - MANUFACTURING OF SOLUTION POLYMERS - Google Patents

Description

Copolymers of conjugated dienes (1,3-butadiene and isoprene) with styrene, which are prepared using lithium alkyls in hydrocarbon solvents, are known to have a graduated block structure; see DJ Kelley and AV Tobolsky, "J. Am. Chem. Soc.% 81, (1959),. page 1597 and I. Kuntz," J. Polym. Sci. ", 54, (1961), page 569. In the case of a copolymerization carried out with the aid of an equimolar mixture of butadiene and styrene, the butadiene is initially consumed more rapidly than the styrene. When the butadiene concentration has then decreased sharply, the styrene is consumed more rapidly In this type of polymerization, if there is no termination, the styrene is incorporated into the polymer chain, which already contains a segment consisting essentially of butadiene units, resulting in a graduated block copolymer with about 53 % of the butadiene segments in the trans configuration

609882/1187

GT-871-F j

are present. If a polar compound, such as tetrahydrofuran or diethyl ether, is added to the copolymerization, the reactivity of the styrene increases at the beginning of the reaction, and copolymers with a more random structure are obtained. However, this method for the preparation of random copolymers has the disadvantage that the vinyl content of the butadiene segments - depending on the type of polar compound used - increases from 6 to 10% to 70 % or more and that the trans content depending on the used amount of the polar compound drops to less than 55%. Rubber or rubber types with. however, relatively high vinyl contents derived from butadiene are not very useful for certain applications in tires, ie when they must have good dynamic responsiveness. Various methods have already been discussed which circumvent the formation of polybutadienes with high vinyl contents and still allow the production of random copolymers of butadiene with comonomers (such as styrene). One of these processes consists in incorporating the comonomers into the reaction system during the copolymerization at a certain rate in order to produce a copolymer whose butadiene segments have a microstructure of 5 to 15% vinyl units and 30 to 60 % cis or trans-butadiene units (cf. . U.S. Patent 3,094,512). Another method is to gradually add butadiene (the most reactive monomer) at a rate such that a high styrene / butadiene ratio is maintained during the polymerization. The result is a copolymer whose butadiene units are at least 30 % in the cis configuration and at most 46.4 % in the trans configuration and have a vinyl content of not more than 12% (cf. GB-PS 994 726). A process that does not require any programmed monomer addition is based

609882/1187

on the use of polymerization temperatures from 93 to over 154 ° C (see US Pat. No. 3,558,575); this method gives SBR polymers with a trans content of 49.1 to 52.7 %, a vinyl content of 9.9 to 10.6% and a heterogeneity index ^ - of 2.65. Organometallic compounds of Cs, Rb, K or Na and their salts with alcohols, phenols or carboxylic acids, their carbonates, the analogous sulfur compounds and amines have already been used with organolithium compounds for the production of random copolymers whose butadiene segments have a vinyl content of 8.8 to 26, 9 % and a trans content of 45.8 to 58.2 % (see US Pat. No. 3,294,768). If polar substances as such, such as oxygen, water, alcohols or primary and secondary amines, are incorporated in such systems in the presence of an alkyl-substituted aromatic diluent, liquid random copolymers are obtained (cf. US Pat. No. 3,324,191), whereby the proportion of the organolithium compound can be reduced. It has been shown that alkali tert-butylates (with the exception of lithium tert-butylate) effectively accelerate the copolymerization of styrene and increase the overall rate of copolymerization. In the butyllithium-initiated copolymerization of butadiene with styrene, which is carried out in the presence of lithium tert-butoxide, the block copolymer obtained shows a negligible dependence of the styrene content on the degree of conversion; see CF. Wofford and HL Hsieh, "J. Polymer Sei.", 7, Part A-1 (1969), page 461. According to US Pat. No. 3,506,631, aliphatic or aromatic phosphites, thiophosphites or amidophosphites in combination with n-butyllithium give random Copolymers with vinyl contents of 10.7 to 15.3 % · The Dutch patent application 69/14452 relates to an improved process for the copolymerization of butadiene with styrene, which is made with the aid of a catalyst

609882/1187

GT-871-F f.

an alkali metal oxide, hydroxide, superoxide or peroxide and an organolithium compound. The copolymers obtained have a random arrangement of the styrene units in a microstructure with a trans content of 52.4 to 55.6% and a vinyl content of 11.0 to 11.6 %. Furthermore, by reacting alkali metals (sodium and potassium) with organolithium compounds, catalysts for the production of solution random butadiene / styrene copolymers with vinyl contents of 7.3 to 25 % and trans contents of 37.1 to 59.1 % were produced (See Australian patent application 48 069 (1968). A catalyst system for diene polymerisation, in which an organolithium compound in combination with a barium compound (such as barium stearate or barium tert-butoxide) is used, is said to be random copolymers of certain dienes and monovinylaromatic Compounds (which are not designated as crystalline) with a vinyl content of 7.8 to 13 % and a trans content of 67.9 % (when using barium tert-butoxide) or 70.5 % (when using of barium stearate) (see Examples 1 and 13 of US Pat. No. 3,629,213) The publication by Ryota Fujio, Minoru Kojima, Shiro Anzai and Akira Onishi (Bridgestone Tire Co., Ltd.) contains certain parallels. ), "Kogyo Kagaku Zasshi", No. 2 (1972), pages 447 to 453, which explains the direct reaction of alkaline earth metals with active hydrogen-containing compounds (in benzene), with the use of barium stearate with an organolithium compound butadiene / styrene copolymers with a trans content of 52.5 9 ^ can be obtained. Barium stearate is referred to in this literature as not very effective; limited molecular weight distributions, but no crystallinity whatsoever, are given for the polymers.

White, tough, thermoplastic homopolybutadienes with a proportion of 92 to 100 % trans-1,4 units and suitable for

609882/1187

GT-871-P {

Floor tiles, golf ball covers and battery cases can be produced by polymerizing butadiene in a hydrocarbon solvent with the aid of a catalyst mixture of an alkyl aluminum dihalide and a β- diketone complex of vanadium, iron or titanium (see US Pat. No. 3,268,500). A mixture of amorphous and crystalline homopolybutadienes, the crystalline fractions of which have 90 to 99 % trans-1,4 units, are produced by polymerizing butadiene with a mixed catalyst of TiCl ₃ , VCl, or VOCl ₅ with aluminum alkyls, zinc alkyls or dialkylaluminum halides according to US PS 3 550 158 produced. In none of these patents are copolymers of styrene described. A mixture of allyl potassium and potassium allyl oxide in an aliphatic diluent is used to polymerize butadiene, a mixed homopolymer having a total of about 64 % trans-1,4 configuration being obtained (cf. US Pat. No. 3,607,851). Although this patent mentions the use of styrene, it does not actually describe copolymerization. According to US Pat. No. 3,642,922, polybutadienes with trans-1,4 proportions of 68 to 79.6 % and vinyl contents of 8 to 20 % and a butadiene / styrene block copolymer with a trans-1,4 proportion of 68 % are used. and a vinyl content of 8% in the presence of cyclohexane or toluene with the aid of an organocalcium polymerization initiator, which is produced by bringing calcium metal into contact with a polynuclear aromatic compound or a polyaryl-substituted ethylene compound in a polyether diluent in the presence of a promoter to provide a fresh calcium surface (such as 1, 2-dibromoethane) (see US Pat. No. 3,642,922). This patent also shows that the butadiene / styrene copolymers produced with the aid of organolithium compounds as catalysts have trans-1,4 proportions of 46 % and vinyl contents of 33 % . Low molecular weight

609882/1187

GT-871- Fr

comprising honey polymers, block copolymers, "conical" (tapered) block copolymers or randoin copolymers of dienes (or dienes with 5.1 to 42.2 % styrene) with trans-1,4 proportions of 59.8 to 77.2 % and Vinyl contents of 6.9 to 13.5 % are produced in hydrocarbon solvents at -30 to 160 ° C. by using an Ate compound of the general formula M ¹ M ² R ¹ R ² R ³ R ⁴ (where M ¹ Ca , Ba or Sr, M ² Zn or Cd and the radicals R represent hydrocarbon radicals) are used (cf. US Pat. No. 3,665,062); the polymers obtained in this way are not found to be crystalline. Polybutadienes with trans-1,4 proportions of 81.7 to 86.7 % and vinyl contents of 6.7 to 9.2 % are obtained by polymerizing the diene in a hydrocarbon diluent at -73.3 to 93.3 ° C (-100 to 200 ⁰ F) using a catalyst mixture of a Organocalciumverbindung and an organoaluminum compound, for example the reaction product of calcium with anthracene and triisobutylaluminum (see., U.S. Patent No. 3,687,916). Although this patent mentions that mixtures of monomers can be polymerized, no copolymers are described. According to US Pat. No. 3,718,703, copolymers of 58 to 52 % styrene and 42 to 48 % butadiene with a trans-1,4 content of 80 to 84 % and a vinyl content of 6 % from the mixtures of the monomers in cyclohexane are used an organometallic compound of Ca, Ba or Sr such as a solution of bis (benzyl) calcium in tetrahydrofuran as a catalyst. Homopolymers of butadiene and random copolymers of butadiene with up to about 25 % styrene, which are crystalline in the stretched state and trans-1,4 proportions from 66.7 to 86 %, vinyl contents from 6.1 to 9.4% and one Heterogeneity index M / M _n of 1.38 to 2.19 are prepared according to US Pat. No. 3,846,385 using various proportions of a barium di-tert-alkoxide and a dibutylmagnesium compound.

609882/1187

GT-871-F Ί

Alfin rubbers made from butadiene and styrene using a mixture of sodium allyl, sodium alkoxide and sodium chloride as a catalyst are described as crystalline with a trans-1,4 content of 70 % and a high vinyl content of 30 % ; See T. Sato, "Rubber Age", January 1970, pages 64 to 71. According to U.S. Patent 3,464,961, increasing the styrene content of the copolymer results in lower crystallinity, while U.S. Patent 3,759,919 teaches that a Increasing the proportion of styrene built into the copolymer obviously does not affect the trans proportion.

It is the object of the invention to provide a new barium alkoxide hydroxide compound suitable for the production of a catalyst and a process for its production. Furthermore, a new catalyst complex of a barium alkoxide hydroxide and an organolithium compound is to be created by the invention, which is suitable for the anionic polymerization and copolymerization of certain ethylenically unsaturated monomers in the presence of a solvent. In addition, the invention is intended to provide a new process for anionic solution polymerization and copolymerization of certain ethically unsaturated monomers with the aid of a catalyst complex composed of a certain barium alkoxide hydroxide compound and an organolithium compound. The object of the invention is furthermore to provide a homopolymer of 1,3-butadiene or a random copolymer of 1,3-butadiene with a total of up to about 15% by weight (based on the copolymer) of isoprene and / or styrene units, wherein the copolymer in the non-blended (non-compounded) and uncured or unvulcanized state after stretching or elongation shows crystallinity and has a low vinyl content and a trans-1,4 content of at least 70 % .

609882/1187

GT-871-F ο

The following detailed description as well as the accompanying drawings and the exemplary embodiments enable this task and the advantages that can be achieved according to the invention to be emphasized more sharply.

From the drawings ζ own ι

Fig. 1 is a diagram showing the dependency of the polybutadiene microstructure (of the butadiene units in a rubbery butadiene polymer produced according to the invention) on the composition, i.e. the Mo! ratio of the Barium alkoxy-hydroxy compound to the organolithium compound in the catalyst complex, illustrated;

Fig. 2 is a diagram showing the gel permeation chromatogram of in toluene using the invention Catalyst produced polybutadienes compared to those produced with the aid of alkyllithium compounds alone Represents polybutadiene;

3 X-ray diffraction recordings of polybutadienes according to the invention with a high trans content for various percentage elongations; and.

4 X-ray diffraction recordings of butadiene / styrene copolymers according to the invention (5% styrene content) with a high trans content at various percentage elongations.

It has been found that a polymerizable vinyl monomer having an activated double bond and up to 14 carbon atoms and free of groups that would destroy the catalyst complex be polymerized under inert conditions in a hydrocarbon solvent at a temperature of about -90 to 100 ^0C can, by acting as a catalyst in a low, for the poly-

809882/1187

GT-871-F «ί

merization of the monomer sufficient amount a complex of

Ba [4O-CR) _a 4OH) _b ] ₂ (1)

^N R

where at least one of the radicals R is a methyl or cyclohexyl group and the remaining radicals R are identical or different and are alkyl or cycloalkyl radicals with 1 to Represent carbon atoms, the a / b molar ratio being from about 99.5: 0.5 to 88:12, and

R ¹ Li (2)

where R ^{1 is} a normal, secondary or tertiary alkyl or cycloalkyl radical having 2 to 20 carbon atoms, the molar ratio of (1) to (2), based on barium metal and lithium metal, being about 0.30: 1 to 0.75: 1 and the solvent dissolves both the monomer and the polymer is used.

The catalyst complex according to the invention is particularly suitable for the production of rubber-like 1,3-butadiene homopolymers as well as copolymers of 1,3-butadiene with up to about 15% by weight of styrene and / or isoprene units.

These butadiene polymers show stress-induced crystallization at room temperature, so that they during manufacture of rubber or rubber products have adhesive power. For example, they show construction tack and do not require any separate tackifier to be adhesive.

Furthermore, these butadiene polymers have "green strength". (Strength in the uncured or unvulcanized state), which with its crystallinity in the stretched State at room temperature and their molecular weight

- 9 _

609882/1187

GT-871-F JO

distribution related. The copolymers are also in the unstretched or unstretched state at room temperature essentially amorphous, which is beneficial for tire rubber. The fact that these rubbers crystallize and have good green strength, makes them also suitable as contact adhesives.

In particular, the rubbery homopolybutadiene and the rubbery random copolymers of 1,3-butadiene with up to about 15% by weight (based on the total copolymer) Styrene and / or isoprene units which are produced according to the invention have the following properties:

a) determined by differential thermal analysis freezing or glass transition temperature of about -80 to -100 ⁰ C;

b) a crystal melting point (maximum values) determined by differential thermal analysis in the unstretched Condition from about -10 to 43 ° C;

c) a trans-1,4 content of about 70 to 81 % and a vinyl content of the butadiene units of up to about 12 %;

d) a heterogeneity index of about 4 to 40 ,.

e) a number average molecular weight of about 20,000 to 300,000;

f) Crystallinity after stretching in the unmixed and uncured or unvulcanized state based on the X-ray diffraction values and

g) Green strength and tack or building tack.

- 10 -

609882/1 187

GT-871 - F AA

The following are the details and preferred embodiments the invention explained in more detail.

The barium tert-alkoxide hydroxide salt is obtained through Implementation of barium metal (preferably in finely divided form and in a stoichiometric proportion) with a tertiary Carbinol and water in liquid ammonia or an amine solvent for the barium at a temperature of about -1OO ° C to the boiling point of the solvent. Specific Examples of suitable tert-carbinols are tert-butanol, 3-methyl-3-pentanol, 2-methyl-2-butanol, 2-methyl-2-pentanol, 3-methyl-3-hexanol, 3,7-dimethyl-3-octanol, 2-methyl-2-heptanol, 3-methyl-3-heptanol, 2,4-dimethyl-2-pentanol, 2,4,4-trimethyl-2-pentanol, 2-methyl-2-octanol, tricyclohexylcarbinol, dicyclopropylmethyicarbinol, dicyclohexylpropylcarbinol and cyclohexyldimethylcarbinol and mixtures thereof. These tertiary carbinols have the general formula

HO-CR
^X R

in which at least one of the radicals R is a methyl or cyclohexyl group and the remaining R radicals are each identical or different alkyl or cycloalkyl radicals with 1 to 6 carbon atoms, such as a methyl, ethyl, propyl, isopropyl, amyl or cyclohexyl group. Preferably all radicals R of the tert-carbinol are methyl groups.

The water content of the water / tert-carbinol mixture is in the range of about 0.5 to 12 mole percent, preferably about 2.5 to 10 mol%, based in each case on the mixture.

As a solvent for the production of the barium alkoxide hydroxide One component of the catalyst is liquid ammonia

- 11 -

609882/1 187

or a saturated, non-polymerizable, non-chelating one aliphatic, cycloaliphatic or heterocyclic, primary or secondary monoamine or polyamine (or mixtures thereof) having 1 to 12 carbon atoms and

1 to 3 nitrogen atoms, which up to the boiling point of the solvent and in the pressure range of about 0.25 to 10 atmospheres is liquid in the temperature range from about -100 ⁰ C. Specific examples of such amines are methylamine, dimethylamine, ethylamine, n-propylamine, n-butylamine, n-amylamine, n-hexylamine, ethylenediamine, pentamethylenediamine, hexamethylenediamine, di-n-propylamine, diisopropylamine, diethylamine, cyclohexylamine, N-butylcyclohexylamine, N-ethylcyclohexylamine, N-methylcyclohexylamine, diethylenetriamine, cyclopentylamine, diamylamine, dibutylamine, diisoamylamine, diisobutylamine, dicyclohexylamine, piperidine, pyrrolidine and butylethylamine and mixtures thereof. Lower molecular weight amines are preferred, since smaller amounts are then required to solvate the metal. The ammonia or amine is preferably used in the pure state. However, one can also use commercial grades, provided that these are no more than about

2% by weight by-products or impurities (such as triamines, other alcohols or water), which must be taken into account in the manufacture of the barium salt. That Ammonia or amine should be freed from any substances that impair the effectiveness of the barium salt as a catalyst component were affecting. The amine should be a solvent for the barium or this at least partially so that it is with the tert-carbinol / Water mixture can react.

In the manufacture of the barium tertiary alkoxide hydroxide salt use an amount of the ammonia or amine solvent sufficient to dissolve the metal. That Amine or ammonia is preferably used in excess

- 12 -

609882/1187

GT-871-F 4 \

puts. When the catalyst production is at. low Temperatures takes place, you do not need any pressure equipment. However, one can use this and the production of catalysts at pressures of about 0.25 to 10 atmospheres (depending on the vapor pressure of the respective amine solvent) make. When producing the catalyst, it is advantageous to keep the reaction mixture in the process of addition and reaction to keep the reaction components moving. Furthermore, there is preferably always one above the reaction mixture inert atmosphere, such as that of helium, neon, or argon; maintain so that contact of the product with the air is avoided. Of course, you can also replace the inert gas use the vapor of the organic compound and / or the amine as an "inert atmosphere". It should be closed Reactors are used. It is not advisable to use the barium di-tert-alkoxide hydroxide in bulk (without Solvent) or in the presence of benzene, since the reaction in these cases is slow and insufficient runs quantitatively and since benzene or its residues can interfere with the subsequent polymerization.

After the barium salt has been prepared, the amine or Ammonia is separated off, for example by distillation, vacuum evaporation or solvent extraction, whereby one Uses temperatures, pressures and solvents that will not damage the barium salt. You can use the amine or Simply evaporate ammonia from the salt, remove any unreacted carbinol, and · the salt after it for example dried at about 50 ° C in vacuum, in one or more aromatic hydrocarbon solvents (such as benzene or toluene) dissolve. Because the proportion of the barium salt solution in relation to the other materials is so small, the aromatic hydrocarbon solvent used for the salt need not necessarily be used correspond to the polymerization solvent; preferential

- 13 -

6098827 1 187

GT-871-F _ήΙΙ

but wisely this is the case. In general, they are diluted Solutions of the barium salt in the aromatic hydrocarbon solvents for injection into the Polymerization reactor preferred.

The yield of the barium salt (based on the increase in weight of the barium) can be around 95 to 100 % . The solution of the barium salt in the aromatic solvent can be prepared and used. However, the solution is usually left to stand overnight to allow a precipitate to settle out. About 30 to 85 wt -.% Of the barium salt are as active catalyst component in the solution phase. The solution phase can be separated from the solid phase by decanting, filtering or centrifuging. Although the solid fraction or precipitate is not suitable as a catalyst component, it can be mixed with the solution phase (or dispersed in it) and used in this form in the polymerization. It must be taken into account that barium is insoluble in benzene, barium hydroxide is insoluble in benzene and toluene, and barium di- (tert-butoxide), for example, is sparingly soluble in benzene.

The obtained barium salt has the following general formula

in which the molar ratio a / b is about 99.5: 0.5 to 88: 12, preferably about 97.5: 2.5 to 90: 1.0, and the R radicals have the meaning given above. Preferably the radicals R represent methyl groups. Mixtures of the barium salts can also be used according to the invention will.

The barium salts can also be represented by the general formulas below

- 14 -

60988 2 / T187

θ ^ R θ R

Ba ²⁺ [4O-C ~ R) _a 4OH) _b ] ₂ or Ba (-0-CR) ₂ · Ba (OH) ₂

^X R

be reproduced.

The barium tert-alkoxide hydroxide salts according to the invention as such do not constitute effective catalysts for the polymerization of butadiene or mixtures of butadiene with styrene and / or isoprene, but result in combination with the organolithium component rubber-like polymers with a high trans content and high molecular weight.

The organolithium compound used according to the invention has the following general formula

R ¹ Li

in which R 'denotes a normal, secondary or tertiary alkyl or cycloalkyl radical having 2 to 20 carbon atoms. Specific examples of organolithium compounds are ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, isobutyl lithium, sec-butyl lithium, tert-butyl lithium, n-amyl lithium, isoamyl lithium, n-hexyl lithium, 2-ethyl hexyl lithium, n-octyl lithium, Cyclopentyllithium, cyclohexyllithium, methylcyclohexyllithium. and 'Cyclohexyläthyllithium and mixtures thereof. The radicals R ^f are preferably alkyl radicals having 2 to 10 carbon atoms.

The molar ratio of the barium salt to the organolithium compound which forms the catalyst complex is approximately 0.30: 1 to 0.75: 1 (preferably about 0.35: 1 to 0.60: 1, especially about 0.50; 1), based on the metals. It is not necessary to use the catalyst before use to prepare in the polymerization, even though you do so

- 15 -

609882/1187

can proceed. If the barium salt and the organolithium compound are mixed in toluene, there is a rapid change in color, which indicates the formation of the complex. If, on the other hand, you use benzene, the color change takes place more slowly. The structure of the polybutadiene remains essentially the same when a polymerization catalyst complex aged 1 to 24 hours is used. However, the trans-1,4 content of the polymers obtained increases by about 5 to 7 % if the catalyst complex is only aged for 15 to 30 minutes.

Before the polymerization, the hydrocarbon solution of the barium salt and the hydrocarbon solution of the organolithium compound can be mixed and the barium and lithium compounds can react or form a complex, the catalyst being formed. The time required for complex formation depends on the reaction temperature and is a few minutes to an hour (or more). The reaction should take place in an inert atmosphere. The reaction components can be heated to temperatures from about 25 to 100.degree. C., preferably from about 40 to 60.degree. C., to accelerate the reaction. When the complex is formed? can be added to the polymerization solvent and (the) monomer (s) or, which is dissolved in _f its solvent the catalyst produced in advance, injecting into a reactor ,, which contains the monomers in the hydrocarbon polymerization solvent dissolved form. '

With the aid of erfindungsgemäßeri catalysts merisierenden to poly vinyl monomer having an activated unsaturated double bond "This is for example _s to $ ene monomers having adjacent to the double bond, a group, the more electrophilic than hydrogen, and not easily cleaved by strong bases leaves. Examples of such monomers are nitriles ₉ such as

- 16 -

609882/118?

GT-871-F ff

Acrylonitrile or methacrylonitrile, acrylates and alkacrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate, Octyl acrylate, methyl methacrylate, ethyl methacrylate, Butyl methacrylate, methyl ethacrylate, ethyl ethacrylate, butyl ethacrylate or octylethacrylate, dienes, such as 1,3-butadiene, Isoprene or 2,3-dimethylbutadiene, and vinylbenzenes, such as Styrene, oc-methylstyrene, p-tert.-butylstyrene, divinylbenzene, Methyl vinyl toluene or p-vinyl toluene, and mixtures of that. These monomers can contain up to 14 carbon atoms have and are free of atoms, residues and the like, which would destroy the catalyst complex. Depending on the one used Monomers, the polymers obtained can be rubber-like, resin-like or thermoplastic.

Monomers preferred according to the invention are 1,3-butadiene and mixtures of 1,3-butadiene with up to about 15% by weight (based on the total weight of the mixtures) styrene and / or isoprene, rubber-like homopolymers and random copolymers being obtained, which after stretching crystalline did. in the unmixed and uncured state, about 70 to 81 % trans-1,4 units, a vinyl content of at most about 12 %, an average molecular weight (number average) up to about 300,000 and the broad heterogeneity index (Mw / Mn ) from about 4 to 40. By varying the composition or microstructure of the butadiene homopolymer or copolymer, a rubber can also be produced which does not crystallize at room temperature, but is subject to crystallization when stretched. This behavior is very similar to that of natural rubber. The invention thus allows the production of polymers which can serve as a substitute for natural rubber in areas of application (such as in tire production). The average molecular weight (number average) is determined by the ratio of the polymerized monomer (in g) to the added organolithium compound (carbon-lithium) (in mol). The conversion to polymer is usually about

up to 100 %.

- 17 -

609882/118?

GT-871-F fg

The temperature can be in the range from about −90 to 100 ^° C. during the solution polymerization. Lower temperatures produce polymers with a higher intrinsic viscosity. Polymerization temperatures from about -20 to 40.degree. C., in particular from about 0 to 30.degree. C., are preferred. The duration of the polymerization depends on the temperature, the proportion of catalyst, the type of polymer sought, and the like. Only small amounts of the catalyst complex are required to carry out the polymerization. However, the amount of catalyst may vary depending on the type of polymer desired. For example, when making high average molecular weight polymers using a given amount of monomer, only a small amount of the catalyst complex is required. Furthermore, since the polymer is a growing (living) polymer, its growth continues as long as monomer is added to the polymerization system, and the molecular weight can thus reach one million or even more. On the other hand, very high molecular weight polymers require a given amount of the catalyst complex very long polymerization times, while the rate of polymerization decreases with lower catalyst concentrations. Polymers with high molecular weight are also in the polymerization reactor r and difficult to handle or process on rubber mills and the like. A suitable range of catalyst complex fraction to achieve readily processable polymer within practical periods of time is about 0.00001 to 0.1 mole (preferably about 0.00033 to 0.005 mole) of catalyst complex (expressed as lithium) per 100 g of total monomer (s) .

Since the polymer dissolved in the polymerization medium represents a growing polymer or the polymerization without

- 18 -

609882/1187

Termination takes place (except if it can be achieved by stopping the addition of monomer or by adding a terminating agent, like methanol, deliberately brings to a standstill), block polymers can be produced by gradually adding monomers or introduce functional groups. Since the growing polymer has a terminal metal ion, can it is converted into a polymer with a terminal hydroxyl group with an epoxide (such as ethylene oxide) and then with water transfer, which by reaction with a polyisocyanate can be crosslinked due to the formation of polyurethane bonds.

The polymerization is carried out in the presence of a liquid aromatic solvent. It is true that bulk polymerization can also be carried out; with this, however, there are heat transfer problems which should be avoided. In solution polymerizations, it is preferred to operate with a polymer solids concentration of no more than about 15 to 20 percent in order to ensure easy heat transfer and processing. The solvents for the monomers and polymers should not have a very labile carbon-hydrogen bond and at least not act as chain terminators to a noticeable extent. Aromatic hydrocarbons which are liquid at room temperature (about 25 ° C.) are preferably used as the solvent. Examples of such solvents are toluene, the xylenes, the trimethyl benzenes, such hemimellitene> (1 ₉ 2,3-trimethylbenzene), pseudocumene, mesitylene, Prenitol (1 ₉ 2,3,4-tetramethylbenzene), IsodurοΓ, ο-, m- and p-cymene, ethylbenzene, n-propylbenzene, cumene, 1,2,4- or 1,3,5-triethylbenzene, n-butylbenzene and other lower-alkyl-substituted benzene derivatives and mixtures thereof. The preferred solvent is toluene. Although you can also use other hydrocarbon solvents such as benzene, hexane, heptane, octane, nonane, cyclohexane, cycloheptane, cyclooctane or mixtures

- 19 -

609882/1187

thereof, can use, their use is not expedient because it does not give the desired high trans content. Polybutadienes produced in benzene and paraffin hydrocarbons, for example, have lower trans-1,4 fractions at crystal melting points below ⁰ ° C. (measured by differential thermal analysis) "

The polymerization should of course be carried out in a closed reactor (preferably a pressure reactor) which is equipped with a stirrer, a heating and cooling device, a device for purging with an inert gas or for pumping in such a gas (such as N ₂ , Ne . Or Ar) is equipped for carrying out the polymerization under inert or non-reactive conditions, devices for the supply of the monomer, the solvent and the catalyst, an aeration device, a device for discharging the polymer formed, among others.

After the polymerization, the catalyst can be inactivated by adding water, alcohol or another suitable agent to the polymer solution. After isolation and drying the polymer can with a suitable antioxidant _v, such as 2,6-di-tert-butyl-p-cresol., Are added. However, the antioxidant can also be incorporated into the polymer solution before it is freed from the solvent.

The polymers produced by the process according to the invention can be mixed and cured or vulcanized in the same way as other plastic and rubber-like polymers. Can be the polymers for example with sulfur or sulfur-donating substances, peroxides, carbon black, SiO _2, TiO ₂₉ Sb ₂ mix O ^ ₉ red iron oxide (Fe ₂ O _3), phthalocyanine blue or green _s tetramethyl "or tetraethylthiuram disulfide or benzothiazyl disulfide * Further, the polymers are stabilizers, antioxidants,

- 20 -

609882/118 7

Incorporate UV absorbers and other anti-degradation agents. Finally, the polymers can be combined with other polymers, such as natural rubber, butyl rubber, butadiene / styrene / Acrylonitrile terpolymers, polychloroprene, SBR rubber or polyurethane elastomers.

The polymers produced according to the invention can be used to produce protective coatings for textiles, bodywork and engine mounts for automobiles, seals, treads and carcasses for tires, drive belts, hoses, shoe soles and insulation for electrical wires and cables as well as plasticizers and polymeric fillers for other plastics and rubbers. With high Sulfur content, hard rubber products can be produced.

The following examples are intended to explain the invention in more detail. but without restricting them.

example 1

Production of barium compounds Experiment 1

75.4 milliequivalents (5.18 g) of barium metal are mixed with 500 ml of monomethylamine containing 7.55 milliequivalents of distilled water. The commercial monomethylamine was first distilled off from a sodium metal dispersion. The reaction mixture is cooled to -708 with vigorous stirring ° C, whereby it assumes a deep blue Par-: .- "■ be. About 10 % of the available barium reacts with water. A 3 molar benzene solution of 69.4 milliequivalents of anhydrous tert-butanol is gradually fed into the reactor containing barium, water and methylamine. In doing so, the blue color changes immediately, and so does it

- 21 609882/1187

a gray suspension is created. The product is obtained by relaxation or flash distillation of the monomethylamine. 10.31 g of a gray-white powder are obtained. About 98 % of all barium metal was converted to barium salts.

A solution of the barium catalyst is prepared by adding 680 g of water-free toluene .. The proportion of soluble barium salts is 55 % of the total product. The total alkalinity of a hydrolyzed portion of the clear, colorless solution is 0.0572 Mi 11! Equivalent OH per g or 0.8% by weight of barium salts.

Other, similar preparations are made using different proportions of water. the trials concerned are designated as Trial 1A, 1B and 1C.

Attempt 2

It is barium tert-butoxide in the presence of methanol and tert-butanol produced in distilled methylamine. That Procedure corresponds to that of experiment 1, except that anhydrous Methanol is used in place of water.

81.4 milliequivalents barium metal are mixed with 500 ml of monomethylamine, which is distilled off by flash distillation of sodium · ⁵ .wurde offset. A solution of 74.2 milliequivalents of anhydrous tert-butanol and 9.2 milliequivalents of methanol is then fed into the reactor. The blue color of the solution changes instantly, giving a gray suspension. After the monomethylamine has been separated off, 11.58 g of a gray-white powder are obtained. The total alkalinity of the clear, colorless toluene solution is 0.104 milliequivalents / g (1.45% by weight soluble barium salts).

- 22 -

60988 * 2/1 187

Attempt 3

Barium tert-butoxide is placed in commercially available monomethylamine here. 72.8 milliequivalents of barium metal will be with 500 ml of commercially available monomethylamine, which is in the vapor form from a cylinder containing the liquefied gas was withdrawn, added.

The solution color of the barium in commercially available methylamine is a light, greyish blue. The solution is added with a mixture of 80.9 milliequivalents of tert-butanol I in benzene. 10.47 g of barium salts are obtained, which indicates a quantitative conversion of the metal to barium salts of methanol, Corresponds to water and tert-butanol (see Table I).

The total alkalinity of a solution of this salt in toluene is 0.088 milliequivalents / g.

Commercial methylamine, as supplied by Matheson Gas Products, is made from methanol and ammonia; see "Matheson Gas Data Book" (1966), page 192. The tested purity of the liquid phase is 98 %. According to the manufacturer's information, the main impurities in the liquid methylamine are water (0.8 %) and di- and trimethylamines 1.4 %) ', see "Matheson Gas Data Book" (1966), page 353. However, the commercial product also contains some methanol. When barium is dissolved in commercially available methylamine, it reacts with methanol and water. Show the IR spectra of the barium salts (in the form of frfujol gauze)

—1 —1

strong absorption bands at 1065 cm and 3580 cm for the carbon-oxygen or oxygen-hydrogen stretching frequencies the methylate or hydroxyl group.

- 23 -

609882/1187

Attempt 4

Barium tert-butoxide is produced in anhydrous benzene from tert-butanol and an excess of barium metal filings. 25.03 milliequivalents of tert-butanol are added to a mixture of 72.5 milliequivalents of barium metal and 283 g of benzene. The mixture is stirred vigorously 10 days at 70 ⁰ C. The obtained yield of Bariumtert thereafter. -butoxide is calculated on the basis of the tert-butanol content of the product obtained as 3.38 g (94 %). The total alkalinity of the benzene solution of the barium tert-butoxide is 0.0114 milliequivalents / g. An IR spectrum of a Nujol mull of the product shows only the absorptions of the tert-butyl ether.

The barium salts in experiments * 1 to 4 are produced in an argon atmosphere or in a vacuum. The composition of the soluble barium salts produced in experiments 1 to 4 is shown in Table I. The total alkalinity is determined by acidimetric titration with standard hydrochloric acid (0.1N). The alcohol levels are measured by gas-liquid chromatography using the standard internal method and sensitivity factors for the flame ionization detector. The hydroxyl ion content is calculated as the difference between the total alkalinity and the total alkoxide content. The barium metal used according to the invention has a purity of 99.5 to 99 »7 % (the main impurities are Sr and Ca, Al, Fe, Mg, Mn, Si, Zn and Na are present as impurities to a lesser extent). The barium salts according to the invention can contain up to about 0.5% by weight of bound nitrogen (based on the total salt including the liquid and solid phase) from the amine solvent [such as' ¹ , (CH ^ NH) ₂ Ba]], which, following the reaction which provides the catalyst, is not entirely due to distillation

- 24 -

609832/1187

GT-871-.F JC

tion u, a, has been removed. It should be noted that a complex of n-butyllithium and Ba (CH ^ NH) ₂ , which contains some free Ba, gives a polymer with a microstructure and properties similar to those of Polymerization Experiment No. 10.

- 25 -

609882/1 187

Table I. Composition "of the barium salts dissolved in aromatic hydrocarbons

σ> ο co

Composition of the solution phase (milliequivalents / g solution)

Composition of the barium salt, J / iol-%

Ver
search
No. Total-
alkali-
nity tert.-
Butylate Methylate hydroxide tert.-
Butylate Methylate hydroxide 1 0.057 *) 0.052 0 0.005 91 O "9 2 0.1045 0.0948 0.008 0 92 8th 0 3 0.0883 0.0773 0.002 0.009 88 . 2 10 4 ■ 0.0114 0.0119 0 0 100 0 0 1A 0.028 0.0273 0 0.0007 97.5 O 2.5 1B 0.036 0.0342 0 0.0018 95 O 5.0 1C 0.0463 **) 0.0363 0 0.010 77 • 0 23.0

No apparent change in concentration after 3 months. After 1 month of standing, the original value is 0.090.

ho σ> co ο cn

GT-871-F

Example 2

1,3-butadiene polymerizations are carried out using argon as protective gas in 0.35 l glass bottles closed with a butyl rubber seal. The solvents and monomers are cleaned. by passing them through 5 A 'molecular sieves. The n-butyllithium is obtained in the form of a 1.6 η hexane solution from Föote Mineral Co. and is diluted with benzene to a concentration of 0.2 milliequivalents organolithium compound (carbonlithium) per g. The organo Irithi-um ^ eiialt ■ ·· .- ■ j ti "■ is determined by the reduction of vanadium pentoxide; cf. PF Collins, C. ¥. Kamienski, DL Esmay. And RB" Ellestad, Anal. Chem. 33, (1961), 'p. 468.

When loading the polymerization bottle, first the solvent, then the n-butyllithium, is added to it the barium salt (all with the help of a syringe) and finally the monomer (via a transfer tube or a lock). The amount of n-butyllithium fed is sufficiently large that the in the solvent and in the Polymerization bottle located acid impurities are neutralized (removed) and that in addition the calculated amount for polymerization initiation is present (see US Pat. No. 3,324,191, column 2, lines 1 to 5). '

About 20 g of butadiene are polymerized in 170 ml of toluene at 30 ^° C. with about 0.66 millimoles of n-butyllithium and about 0.33 millimoles of barium salts. Table II shows the percentage degree of conversion and the molecular structure of> polybutadienes which were produced with the barium salts produced according to the experiments described above or with n-butyllithium alone (in the absence of barium salts). ■ ·

+) "Citrate"

- 27 -:

609882/1187

' Table II

Effect of the composition of the barium salt on the MoIe-

The structural structure of the polybutadiene

I. Poly Manuf Molar ratio s Conversion % Diene structure vinyl Maxima ω » I.
ivi meri ment of the Ba ²⁺ ZLi ⁺ *) lung trans ler Kri .dl / g oo station barium gray f / ο
(Hours.) 7th barn- I. Vox OUOll
No. salt
(Attempt
No.) butyl only 55 scnmexz—
Ounkt, oc 0.45 CD
O lithium 100 (9) 8th CO 10 > ^S mm 0.45 78 9 not fixed 4.20 CD 0.46: 95 (27> • ⁶⁴ 9 posed 1.47 CD
ts> 11 1 0.45! 89 (67) 73 9 29, 35 4.35 ■ - «. 12th 2 0.49 84 (21) 66 7th -8th 1.32 k 13th 3 0.52: 84 (21) 76 7th 28, 38 5.22 CO
-α 14th 4th 0.51 100 (72) 76 20th -4 6.67 15th 1A 0.47 y 100 (72) 60 24, 33 not 16 1B ! 1 21 (66) 23, 31. like s 17th 1C : 1 -24, 46 sen, ! 1 Chews \ 1 schuk : 1 : 1 : 1

The active molar ratio of the total barium ions to the organolithium compound (carbon-lithium) (Ba ^ ⁺ / Li) available for the polymerization; the organolithium compound required for neutralization or titration is not taken into account.

Q
oo

N) CD CO O cn CD CJO

The molar ratio of the barium salts to the n-butyllithium is based on the total alkalinity of the soluble barium salts and the concentration of the organolithium compound measured by the oxidimetric method on the basis of vanadium pentoxide; see Anal. Chem. 33, (1961), p. 468 (loc. Cit.). . ·

The copolymer composition and percent polybutadiene microstructure are determined by IR analysis. The trans-1,4-proportion or vinyl content is determined from the absorption bands at 967 cm "and 905 cm". The cis-1,4-fraction is calculated as follows: 100 % - (% trans-1,4-fraction + % vinyl content) * The intrinsic molar viscosity numbers are calculated in benzene at 25 ° C (0.3 g of polymer in 100 ml benzene). All thermal transitions are determined by differential thermal analysis at a heating rate of 20 ° C / min, starting at about -170 ° C. . ··· '.

According to the thermal transition measurements, only the polymerizations with n-butyllithium and the hydroxyl anion are formed containing barium salts (experiments 11, 13, 15 and 16) polybutadienes with crystal melting points near room temperature. The excitation of butadiene with n-butyllithium and pure barium tert-butoxide (experiment 14) or with the Barium tert-butoxide containing methylate ion (experiment 12) is not suitable for the production of crystalline polybutadienes. The molecular structures of those produced with n-butyllithium and the barium salts produced according to Experiment 11 and Experiment 13 Polybutadienes are practically identical. In each case the barium salt contains the hydroxyl ion. The in accordance with Run 13 produced a small amount of incorporated methylate barium salt (2 mol-50 apparently affects the structure not. With butyllithium and barium tert-butoxide / barium hydroxide Polybutadienes are very tough, elastic materials, which easily make foils or films.

- 29 -

60 9 8 82/1187

ben. In comparison, provide with corresponding concentrations of n-Bütyllithium in the presence of pure barium tert-butoxide or barium _{e-tert-butoxide} "and Bariuinmethylat generated polymer materials with low viscosity. The polybutadienes having high molecular weight have a reduced cold flow, presumably, according to their broad molecular weight distribution (determined by gel permeation chromatography or GPC) ₀

Table I shows that hydroxide salts reduce the solubility of Barium tert-butoxide in aromatic solvents as well as methoxide salts increase. However, it can be seen from Table II show that the hydroxyl ion is capable of the trans-1,4-portion of polybutadiene, thereby obtaining a crystalline high molecular weight polymer will.

The barium tert-butoxide hydroxide salt can indeed be a very low molar proportion of the barium methylate salt (or methylate salt), which is less than the Hydroxide portion is included; however, this is not particularly useful.

The number average molecular weight was found to be that with the complex of n-butyllithium and the barium salts produced polymers in the ratio of the weight of the polymer produced to the moles Butyllithium corresponds. The molar ratio Ua / Ü is based on the: 'ratio -of · moles of total alkalinity of the · soluble Barium salts (half the milliequivalents of the titratable base) to the moles of the organolithium compound. the percent conversion is calculated from total solids after removal of solvent and unreacted Monomers by flash distillation. A repetition of the polymerization experiment No. 12? with a Barium salt, which is made using tert-butanol

- 30 -

609882/1187

and tert-amyl alcohol was produced instead of methanol (Experiment 2) "gives similar results"

A polymerization of the type described in this example, in which n-butyllithium and a physical mixture of separately prepared Ba ('tert-butoxide) p and Ba (OH) ₂ in a molar ratio Ba ^{+ 2} / Li ⁺ of about 0.5 : 1 is used, results in a polybutadiene with a low molecular weight and a low proportion of traris (see table

ix). ■ .- ■■ · ■ -. ■

Example 3

This example explains the usefulness of the tests 1 and 3 described barium salts for the preparation of crystallizable copolymers of butadiene with Styrene and isoprene, which are polybutadiene segments with a high trans content with a statistical comorino sequence or distribution exhibit,. The polymerization conditions correspond those of Example 2. The styrene and isoprene are fed immediately after the butadiene.

The comonomer distribution of the SBR rubbers produced according to the invention is statistical, such as nuclear magnetic resonance measurements, Investigations of the oxidative degradation with osmium tetroxide and tert-butyl hydroperoxide as well as the determination of the freezing temperature show by differential thermal analysis.

Table III shows the results.

- 31 -

609882/1 187

CD
O
CD
OO
CO

Molecular structure of Bound
denes
Comono-
meres
(Gev .-%) Table III Manuf
ment of the
barium
salt
after
search no. Styrene vinyl and isoprene 3.10 Molver
ratio
Ba ² VLi ⁺
■ X * *) ω Comono-
meres 5 1 % Butadiene
micro structure 8th Maximum
crystal
melt
point, ⁰ C 2.18 0.48 71-F Poly-
meri-
station
attempt-
No. Styrene 15th Copolymers of butadiene with 1 trans 8th 13th 0.68 0.51 20th Styrene 25th g total
monomers
per mmol
n-BuLi *) 3 76 11 -6 4.40 0.88 21 Styrene 5 31.0 3 71 8th not
fixed
represents 4.72 0.51 22nd
I.
OJ Isoprene 11 36.2 1 71 8th 34 3.16 0.46 A- ι 23 Isoprene 10 73.9 1 77 10 3 0.50 Cw 24 Isoprene 32.4 77 -1 25th 36.5 75 38.8

n-butyllithium

see the footnote in Table II.

CD CO O

cn cn co

Table III shows that SBR copolymers with a styrene content. of about 5 % have crystal melting points at or slightly below room temperature _e Melting points slightly below room temperature are advantageous. When deforming. The material lies in the amorphous at room temperature. State before. During elongation, stress-related crystallization occurs when the melting point of the crystallites increases. The presence of crystallites. In, deformed rubber leads to an increase in its green strength and tackiness (adhesion). Both properties are favorable for tire production and provide characteristic features of the polybutadiene rubbers according to the invention. high trans content.

The crystalline melting point of the polybutadiene copolymers with a high trans content increases with increasing comonomer content according to Flory's equation for melting point depression away; see P. J. Flory, "Principles of Polymer Chemistry", Cornell University Press, Ithaca, N.Y., (1953), page 563 »

According to Flory's equation, the high trans content copolymer with 5 % styrene should have a melting point of 17 ° C. The differential thermal analysis gives a melting point of 13 ^° C. The melting point values and the intensities of the melting endotherm. decrease with increasing styrene content until no melt transition is found in the differential thermal analysis at a styrene content of 25 %. ·

Example 4

There are several attempts using different molar ratios of the barium salts to n-butyllithium carried out. N-Butyl-

- 33 -

6 0 9 8 8 2/1187

lithium; the barium salts are made using tert-butanol and water according to experiment. 1 generated. The polymerization charge corresponds to that of Example 2. Table IV shows the results.

6 0 9 8 8 2/1 1 87

Table IV

Influence of the molar ratio of the barium salts to the n-butyllithium
the microstructure of polybutadiene

t Polymeri catalyst 0 Molar ratio : 1 I.
Previous year station (Millimoles) 0.17 Ba ² VLi ⁺ -X-) ; 1 . VJl try—
No. BuLi barium salts 0.26 0 ; 1 I. 30th 0.76 0.33 0.24 : 1 CD.
O 31 ■ 0.72 0.34 0.39 : 1 CO
00 32 0.66 0.41 0.46 : 1 CO
ΪΌ 33 0.72 0.47 0.54 t 1 I ^^ 34 0.64 0.67 0.68 . 35 0.61 0.75 co
-4 36 0.63 0.96 37 0.70

Degree of conversion

100 95 97

Diene structure % Vinyl % trans 7th 55 10 59 7th 76 8th 78 7th 78 9 69 12th 63 32 **) 51 **)

see the footnote in the table

The polymer is not soluble in carbon disulfide; the
The diene structure was determined by IR analysis on a cast film.

Table IV shows that the trans / cis ratio in the case of an ■ increase in the molar ratio of barium salts to butyllithium from 0 to 0.5: 1 higher, which is the vinyl content little changes. At molar ratios greater than 0.5: 1, the vinyl content increases, while the proportion of trans-1,4 unsaturation decreases. The influence of the molar ratio on the microstructure can also be seen in FIG. 1, where the Curve for these experiments a maximum of the trans-1,4-portion ..- at a molar ratio of about 0.5: 1. The polybutadienes produced using this molar ratio are characterized by trans-1,4 fractions of about 78% by weight broad molecular weight distributions, intrinsic viscosity numbers of 5.0 and freedom from gel.

The solid line in FIG. 2 illustrates, for example, the broad molecular weight distribution of the hemopolybutadiene from experiment 33, which has the following characteristics: H _n = 41,600, S _w = 753,000 , \ Ζ \ = 18.1 and Qrβ = 4.2. On the other hand, the dashed line in FIG. 2 illustrates the narrow molecular weight distribution of a homopolybutadiene in the production of which only n-butyllithium was used as a catalyst; the characteristics of this polymer are: M _n = 127,000, R ^. = 147 000, \ / ® _n = 1.16 and \ j \ ~ \ - 1.34. The molecular weights are determined by gel permeation chromatography after calibration with polystyrene. The measurement of the intrinsic viscosity numbers is carried out at 25 ⁰ C in benzene.

When using the butyllithium / barium salt catalyst, the polymerization rate is lower than with a comparative polymerization in which butyllithium alone (in the same concentration) is used. However, quantitative conversions are achieved after 16 to 24 hours at 30 ^° C. in toluene. The times can be shortened by increasing the temperature. Ba / Li -Molver-

. - 36 -

60 9882/1187

ratios greater than about 0.75: 1 result in polymerizations with generally non-quantitative degree of conversion and to gel-containing polymers.

Example 5

Homopolymerizations of isoprene are carried out according to the general one Method of example 2 with the complex of butyllithium and barium salts using the according to experiment 3 produced barium salts by. Due to the presence of the barium salt, the rate of homopolymerization decreases while the 3.4 share increases. Table V shows the results. The percentage diene structure is Nuclear resonance determines «The proportion of the 1,2 structure is immeasurably small.

- 37 -

609882/1 187

Table V

Molecular structure of polyisoprene made with butyllithium and barium salts

OD I

Polymerization experiment- « No.

40

41 42

Initiator (millimoles)

Molar ratio

BuLi 0.61

0.61 1.0

Barium salts Ba ²⁺ ZLi * *)

Comparative experiment

0.46 1.0

0.75 1.0

Isoprene,
G

17.4

17.9
27.2

Conversion
degree, %

100

72

65

Diene structure

% 3Λ% ice cream % trans

7.4 65.5 27.1

22.2 29.7 48.1

53.6 10.6 35.8

see the footnote in the table

The polymerization experiments 40 and 41 are carried out at 50 ^° C. in 105 g of toluene, while the polymerization experiment 42 is carried out at 50 ^° C. in 134 g of benzene. In tests 40 and 41 · charged; the Polymerisatiohsflaschen with 17 g isoprene, in test 42 with 27'g isoprene.

K) CD CO O CTJ CD OO

The net increase in the trans-1,4 proportion of the polyisoprene prepared with the aid of the catalyst complex according to the invention in comparison to n-butyllithium - (Table IV) is approximately the same (about 20 %) as for the polybutadiene alone prepared in an analogous manner. In the case of polybutadiene, an increase from 54 to 78 %, ■■ _ in the case of polyisoprene, an increase from 27 to 48 % . Thus, in the presence of the barium salts, both polyisoprene and polybutadiene polymers are present. There is a tendency towards an increase in the trans-1,4-fraction. The microstructure of the polyisoprene produced with n-butyllithium and barium salts, however, does not have a predominant trans-1,4 component. Therefore, crystalline polyisoprenes are not obtained.

Example 6

A physical one related to polymer crystallization A property which is of particular importance for carcass rubber is green strength. These The size of the polymer with a high proportion of trans-butadiene produced with n-butyllithium in the presence of barium salts measured. The polymer has the property of stress-induced crystallization, like the X-ray diffraction analysis and show stress birefringence measurements. . .

The green strength values are obtained from stress-strain measurements on unvulcanized polymers using an Instron tester at room temperature. The forward 'pushing speed is 8.47 mm / sec. The test specimens are prepared kg for 5 minutes by molding Zugfolien at 10O ⁰ C and a ram force of 13,608th The results are shown in Table VI.

-39-

609882/1187

GT-871-

HO

Table VI Green strength

Polymer

Mooney viscosity
ML-4 (10O ⁰ C)

Yield strength, kp / cm2 (psi) ■

Tensile strenght, k / 2 (psi)

BCDE

39 42 72 54

9.00 8.86 - - 1.55

(128) (126) (22)

25.73 27.00 13.85 7.87 0.70

(366) (384) (197) (112) (10)

Elongation at break, % 1433 2320 1338 520 338

2.39 (34)

The green strength (strength of the uncured or unvulcanized and unblended polymers) is in Table VI for the new polybutadiene and "the new SBR polymers (5 % styrene) of the invention and for comparison for natural rubber, SBR rubber, Alfin- SBR and lithium-catalyzed polybutadiene cited "The new butadiene poly-."; · Mers have a higher green strength than natural rubber The tensile strength (in the "green" state) of natural rubber is known to be related to stress crystallization.

The green strength of the new polybutadiene is based on the reinforcement by the elements contained in the unstretched material Crystallites and the stress resulting from the deformation-induced crystallization. It is also to be assumed that the chains having a high molecular weight are subject to a high degree of entanglements, which'zur Contribute green strength.

- 40

6 0 98-82 / 118

Remarks: Ar polybutadiene from. Table II, second

Polymerization using the barium salt from Experiment No. 1 j

B: Butadiene / styrene copolymer (5 % styrene) from Table III, first polymerization using the barium salt from Run No. 1;

C: Alfin-butadiene / styrene copolymer (5 % styrene) "Nippon-Alfin Rubber Co., Ltd", Tokyo, Japan, AR-1510; See "Rubber Age" (January 1970), pages 64 to 71;

D: natural rubber (peptized No. 3 ribbed smoked sheets);

E: solution polymerized polybutadiene, The Firestone Tire & Rubber. Co.,. Diene 55-NF;

F: SBPI 1500; emulsion polymerized copolymer of 1,3-butadiene and styrene (about 23.5 % bound styrene).

Example 7

The adhesive strength of the new, high trans content having SBR rubbers (5 % styrene) and polybutadiene rubbers of the invention is compared with that of rubbers which crystallize on deformation ^ "natural rubber, polybutadiene with a high cis content (99 % cis -1,4), trans-Polypentenamer and Alfin-SBR J as well as amorphous, non-crystallizing polymers (SBR 1500 and lithium-catalyzed polybutadiene) compared see; contact

- 41 -

609882/1 187

pressure 0.22 MPa at a cutting speed of 0.424 mm / sec. The test specimens consist of crude (nichtabgemischten and uncured) polymers, which are pressed between sheets of polyester (Mylar) at 100 ⁰ C and punched out to a size of 5.08 cm 0.64 cm χ. The actual bond strength values shown in Table 11 represent the difference between the apparent bond strength (rubber versus rubber) and the value obtained for rubber versus stainless steel.

- 42 -

609882/1187

GT-871-F

Table VII

2630S68

Adhesion strength of amorphous and crystallizable rubbers (Monsanto Tel-Tak)

Poly- M 25 ° C meres benzene

VIII
IX

2.76

3.56 3.65 2.52 2.50

2.44 2.06

Maximum crystal melting point, ■ ⁰ C

28 -6 42 25

not determined

not determined

Adhesive strength

apparently really kp / cni ^ (psi) kp / cm ^ Cpsi)

2.67 (38)

2.39 (34)

1.90 (27)

1.27 (18)

1.20 (17)

1.69 (24)

0.91 (13)

2.46 (35) (0.24 MPa)

(32) (15) (9) (7) (24)

2.25 1.05 0.63 0.49 1.69 0.42

(6)

1.55 (22) 0.28 (4) 0.28 (4) 0.21 (3)

Remarks % I

II

III

IV

VI

VII

trans polypentenamer,
Paint factories Bayer AG, TPR;

Natural rubber, "same as D, in '.' Table VI; '

SNAT-I Progetti's, Italy, cis-1,4-polybutadiene; (99 % ice);

Alfin polymer is the same as C in Table VI; ■ -

High trans SBR, same as B in Table VI;

Mixture of equal amounts by weight of natural rubber (II) and SBR with a high trans part (V); ■ ■ ■

Solution Polybutadiene, Firestone Tire & Rubber Co., same as E in Table VI;

VIII SBR 150O ₅ same as F in Table VI5

IX polybutadiene, same as A in Table VI «

- 43 -

60988 2/1187

The results of Table VII show that the bond strength of high trans SBR is higher than that of non-crystallizing polymers but less than that of stereopolymers that crystallize upon elongation. The adhesive strength of SBR rubber with a high trans content is roughly the same as that of AIfin-SBR «. Alfin rubbers are crystalline at room temperature and are subject to deformation-related crystallization. The lower bond strength values of Alfin-SBR and SBR with a high trans content compared to natural rubber can be related to the lower degree of crystallinity achieved by the deformation. The bond strength of the mixture of natural rubber and SBR with a high trans content lies between the values of homopolymers concerned.

Example 8

It is made using n-butyllithium and butadiene polymerized a barium compound according to Example 2 with the exceptions shown in Table VIII.

60988 (2/1187

Table VIII

Polymeric
sa «

tions «
ver «
suoh, -Nr,

Mole

VJI
I.

Making the
Barium compound

Poly "Poly" microstructure

meri «meri« poly «from« the servants »

*** 2 sations "sations" meri "beu"

Ba / solutions. "Tempera" sat ions "te ■" ■

Li ⁺ *) middle door, ^Q C duration % trans Vinyl ice

i (tert-butoxy) 0.5? 1 ._3? E> luo! 30 barium ;. Herst, un «. .
known (cf., US ~ P3
·? 629 215, ex. 18)

pure. la (tert, «BuO) n 0.5» 1, .Soluene- "'80 **) (M) ■ ^ά .

pure Ba (tert, "BuO) _a O, 48s1.-4Bo" 3.ti & l

pure Ba (tert "-BuO) p, 0.49s 1. '! Pblttoa,' ^ O Table I ₁ experiment
No. 4 (Tab, II. Polyme "
ris, verse, no, i4) (her «
died in benzene)

Ba (tert, -BuO) ₂ , contained 0.5: 1 · '-. ICöluene · '50

tend methylate and hy "
droxid, tab, i, try
No. 3

Ba (tert. «BuO)« «hydroxide, ·

Table I, experiment number 1 0.45x1. Toluene - 30 (Table II, Polymerisa «
test number 11)

min 88.3 62.3 9.5 28.2 not

indicated «

min 86.8 57.6 10.5 31.9
H _s 51.0 57 1Q

0.45

Medium viscosity oil

Hrs. 84

66

25 1.32

Hour, 96

71

20 1.12

Hour 95

78

14th

4.20 O'cn

SLJkL S

See the footnote in Table II for 20 g of Bd / 0.9 mmoles of BuLi

Remarks: M: Made by converting barium

metal with tert-butanol in von ¥ aster and amine free liquid ammonia. That Ammonia is distilled off before use in the polymerization and replaced by the conical hydrogen solvent j

N: monomethylamine is of ribbon-shaped

Sodium distilled off (flash distillation). The pure, condensed amine is mixed with barium and tert-butanol. The components are allowed to react. The amine is then distilled off from the barium di- (tert-butoxide), which is suspended in benzene. The clear portion of the benzene solution of the barium di- (tert-butoxide) is used as a catalyst (the total alkalinity is 0.0127; the barium salt consists of 100 % tert-butoxide).

These results show that pure barium di- (tert-butoxide) those achievable using the salts according to the invention does not provide improved results.

Example 9

It is butadiene polymerized using n-butyllithium and a barium compound in toluene at 30 C according to Example 2 with the exceptions shown in Table IX.

- 46 -

609882/1187

Table IX

Poly-
meri- Making the MoI- Poly-
meri- the end sa-
functional Barium bond ver—
holds- station prey
(Convert ver ms duration, lung search- BaJ ⁺ / Hours. Degree), No*. Li ⁺ *) %

60 Ba (tert-BuO) «hydroxide, Table I, Vers.Nr.1 (Table II, Polymerization Vers. No. 11)

61 physical mixture of Ba (tert-BuO) ₂ and Ba (OH) ₂ (0)

5: 1

0.60: 1

υ ».62 Ba (tert-BuO) ₂ + 10 % 0.51: 1 *

H ₂ O

(P)

26th

Microstructure

the service unit- maximum. ,

th crystal

- -. - 'melting

trans vinyl ice point, ⁰ C

8 14 29, 35 4.20

63. 8 29

-19

. 9 · '29 r-19

0.83

0.68

. see the footnote in Table II

\ o cn

IfP

GT-871-F 263Q568

Comments: O: The barium di- (tert-butylate) is like

at M in Example 8. The barium hydroxide is made in the same way generated, but using water instead of tert-butanol. Afterward a mixture of the two compounds is prepared and used in the polymerization experiment.

P: The barium di (tert-butoxide) is used in the same Made in the same way as for M in Example 8. The water for implementation with the Ba (tert-BuO) p is in the form of a mixture with the polymerization solvent (Toluene) added.

The hydroxyl contents of the barium compounds or salts of the polymerization runs Nos. 60, 61 and 62 are approximate same.

Example 10

Butadiene is combined with styrene according to the general method of Example 3 in toluene with the aid of n-butyllithium and barium distearate copolymer! sized »The polymerisation conditions and the results are shown in Table X.

- 48 -

809882/1187

GT-871-F

• Η

-P

co cd

Φ -P

CQ p

Φ
H
H
Φ

CQ

ι ι ο u

> vH · Η Φ Χ} H UP PP

ο φ cd cdco

CM β CQ tJ

ι ι

CQ Cd

β in

ο Φ

ί> ,. Η · Η Pl ₁ PO
H kP S-PO
O Φ Cd Φ
Οι S CQ + 3

Ι · Ρ
H ^ H CQ
O Φ: cd · Η

Cd-H

QO β
P.

Ö
• Η

• Η
Sh

CD

I.

Ö I

rifn I OShU
O Φ Cd · Η Φ P
CU S CQ + 3> CQl

CvJ

CO

IA O

CM CM

LA CM

CM

νο "

IA

CD,

νο CM

CM

VO

cn

CM

CO

IA

• ν

- I.

»• ■ ν cd • PCM cd φ U Ο> · Η cd CM £

S pco

φ Ρ-.Ο0

CdCO CQ Q) CQ Ϊ2 CQ οΟ

O IA

• Ρ cd

cd U

CD

φ +> ■ Ρ ß

CQ CD -H QO

ti cd a ω

PfrJ • Η I ^ CO

CdO

C- - 49 - HH

Φ HH Φ • 3

-P O

CQ

Φ • Η

609882/1187

GT-871-F SO

Comments: Q: Presumably statistical order, there one

Value of 0 % for the yield of the oxidative degradation product is given (column 12, lines 53 to 54 and column 10, lines 1 to 6).

R: block copolymer; determined by sampling during the conversion - % polymer solids and monomers as a function of the elapsed polymerization time. The styrene is mainly polymerized in the conversion range from 60 to 96 % . Charge ratio: 25 g total monomers / 1 mmole n-butyllithium.

The difference in the polymerization temperatures should not affect either the microstructure or the styrene arrangements. significantly influence, (see page 4 ,, lines 21 to 32).

Example 11

A barium salt is prepared analogously to Example 1, Experiment 1; However, the salt contains 5 molar 6 hydroxide. The total alkalinity of the barium salt solution phase is 0.057 milli-equivalents / g of solution. The barium salt solution and the n-butyllithium solution are (I) mixed and aged for 30 minutes at room temperature or (II) mixed and ^{aged at 50 °} C. for 30 minutes. Both in (I) and in (II) the molar ratio Ba ²⁺ / Li ⁺ (cf. the footnote in Table II) is 0.5: 1. Butadiene is then polymerized at 30 ° C. in benzene according to Example 2. Table XI shows the results.

6 0 9 8 8 2/1187

GT-871-F

Sf

Table XI

Polymerization experiment no.

Transformation,

(Hours.)

80 (I) 93 (44)

81 (II) 88 (44)

Diene microstructure

trans vinyl ice

70

68

8 8

22 24

Maximum crystal melting point, ° C

-16 -16

1.43 1.50

In both cases, the polybutadienes obtained are amorphous at about 25 ⁰ C. The results illustrate the difference when using benzene or toluene as the polymerization solvent.

Example 12

Example 1, experiment 1 is repeated, except that liquid ammonia is used instead of monomethylamine. The water / tert-butanol molar ratio is 5:95. The barium salt solution obtained has a total alkalinity of 0.062 milliequivalents / g solution (0.059 milliequivalents tert-butoxide / g solution and 0.003 milliequivalents hydroxide / g solution). The barium salt solution is then mixed with the n-butyllithium solution in such a proportion that a molar ratio Ba / Li ⁺ (cf. the footnote in Table II) of about 0.5: 1 is achieved. With the help of the mixed catalyst solution, butadiene is then polymerized according to Example 2 for 42 hours at 30 ° C. in toluene. A degree of conversion of 93 % is achieved. This gives a polybutadiene having a trans-content of -72% _t a vinyl content of 8%, a cis content of an intrinsic viscosity in benzene at 25 ^Q C of 2.31 and a crystalline melting point of 22 ° C; 37 ° C.

- 51 -

6 09882/1187

GT-871-F SZ

Example 13

A barium salt is prepared according to Example 1, Experiment 1, except that only 5 mol% of water are used. The barium salt has a total alkalinity of 0.04 milli-equivalents / g of solution. With the help of this barium salt and n-butyllithium (molar ratio Ba ⁺⁺ / Li ⁺ ■ about 0.5: 1; compare the footnote in Table II), butadiene is polymerized analogously to Example 2, Experiment 11 in the presence of toluene. Table XII shows the results.

Poly- Table XII Around- 98 (24) Micro structure ice cream Maxima Tg, *) Poly merisa- Wall- 90 (144) 12.6 ler Kri meri- functional lung 17th barn- ' ° c L ^ J sa- Degree, trans vinyl schmp., -91 5.90 functional % 80.4 7 oc -93 7.02 ver tempera- '(hours) 77 6 19.32 search- tur, ⁰ C 29.37 No. 15th 90 5 91

/ Freezing or glass transition temperature.

Table XII shows that higher viscosities are achieved at lower polymerization temperatures. The homo polybutadienes obtained are crystalline near room temperature.

Example 14

A barium salt is prepared according to Example 1, Experiment 1, With the help of this salt, two polybutadienes are made according to

• - 52 -

609882/1187

GT-871-F

Example 2, Run 11 using a Ba ⁺⁺ / Li ⁺ molar ratio (see footnote to Table II) of about 0.5: 1. A homopolybutadiene has a total trans content of 74 %, a vinyl content of 8 % and a cis content of 18% and an intrinsic viscosity of 5.1. The second homopolybutadiene has a total trans content of 75 %, a vinyl content of 8 %, a cis content of 17 % and an intrinsic viscosity of 4.66. 60 parts by weight of the first polybutadiene are mixed with 40 parts by weight of the second polybutadiene, a polybutadiene mixture having an average intrinsic molecular viscosity of 4.9 being obtained. 100 parts by weight of the polybutadiene mixture are then mixed with 0.5 part of stearic acid, 1 part of zinc oxide, 1 part of N-cyclohexyl-2-benzothiazole sulfenamide ("Santoeure", Monsanto Chem. Co.) and 1 part of sulfur. Samples of the Polybutadienmischung are then cured for 20 minutes at 149 ° C (300 ^o F) and cured (Vulkanisationsoptimum). Samples of the vulcanized polybutadienes (no reinforcing agent) are then subjected to x-ray diffraction analysis at room temperature. The vulcanizates of polybutadiene have X-ray diffraction diagrams which are characteristic of crystalline trans-1,4-polybutadienes in the unstretched state; see Fig. 3, image a (outer ring of light or outer band of light). At 100 % elongation (picture b), 200 % elongation (picture c) and 300 % elongation (picture d), the diffraction diagrams show the fiber pattern, which shows oriented crystal areas of the polymer. The pictures illustrate the diffraction rings which are related to the (100) plane of the trans-1,4-polybutadiene crystallites (cf.Liricei-Rend. Sc. Fis. Mat. E Nat., Vol. XX (June 1956) , Page 729).

- 53 -

60.9882 / 1 187

GT-871-F J

Example 15

100 parts by weight of the SBR with 5 % styrene, ie of the copolymer of test 20 from Example 3, are mixed with 1 part of stearic acid, 3 parts of zinc oxide, 1 part of "Santocure" and 1 part of sulfur. Subsequently, cured samples of the blended copolymers for 30 minutes at 149 ° C (300 ⁰ F) (Vulkanisationsoptimum). The vulcanized samples are then subjected to X-ray analysis at room temperature.

In the unstretched state, the 5 % styrene-containing SBR polymer has an X-ray diffraction diagram that is typical of an amorphous material; see. Fig. 4, image a ¹ . 4 further illustrates the crystalline X-ray diffraction diagrams for this copolymer at elongations of 225 % (image b ¹ ), 400 % (image c ¹ ) and 500 % (image d ¹ ). At an elongation of more than 200 % , the intensity of the amorphous halo decreases simultaneously with the appearance of X-ray reflections in the form of equatorial arcs, which indicate the formation of crystallites oriented parallel to the direction of elongation.

Stress-optical measurements have shown that rubber-like vulcanizates of the SBR rubbers according to the invention (5% styrene) with a high trans content are subject to stress-induced crystallization at room temperature, although they are amorphous in the unstretched state at room temperature. In the case of low elongations, no increase in the stress-optical coefficient (ratio of birefringence to stress during relaxation) as a function of time can be determined. However, an increase in the stress-optical coefficient is observed with elongations of more than 200%. In stress-relaxation tests, the ratio of amorphous rubber, which crystallizes in the course of these tests, increases over time.

- 54 -609882/1187

GT-871-F

SS

nis of birefringence to stress ^ "" "The Physics of Rubber Elasticity ", L.R.G. Treloar,. Oxford at the Clarendon Press, Great Britain, 2nd edition (1958), Chapter 10, pages 197 to 234_7. These results show that the rubbers of the invention with high The trans portion represent stress-crystallizing rubbers. The adhesive strength and green strength are related on the crystallizability of a rubber; It has been shown above that the polymers according to the invention these Possess properties.

Example 16

Styrene is polymerized in toluene according to the general method of Example 2. The polymerization conditions and the results obtained are shown in Table XIII. ·

Table XIII

Polyme- Method Mol- Poly- Um-. By GPC

risations- to the merger- wall-specific

attempt- hold- dall, «

No. des- barium- nis- % _r -,.

salt Ba ++ / temp. (Std.) UHJ Li ⁺ *) QC .

100 Ex. 1, 0.49: 1 -20 100 (20) 0.464 47000 Vers. 1

101 Ex. 1, 0.75: 1 30 100 (1/2) 0.420 not vers. 3 measure

Run 100: Charge ratio: 20.5 g styrene / 0.74 mmol

n-butyllithium;

Run 101: Charge ratio: 21.8 g styrene / 0.49 mmol

n-butyllithium. '

'see. the footnote in Table II

- 55 -

609882/1187

GT-871-F & 2630588

The heterogeneity index (Sw / Sn) of the homopolystyrene of the polymerization experiment No. 100 is 2.0. With the aid of the catalyst system according to the invention, 100% conversion of the styrene into polystyrene is achieved ^{in toluene at 30 ° C. within 30 minutes.} On the other hand, butadiene is converted to toluene within 30 minutes at 3O ⁰ C to 5% in the polymer, while within 24 hours at 30 ⁰ C a 100% conversion is achieved.

Example 17

Butadiene / styrene copolymers are prepared according to Example 3, Polymerization test Kr. 20. The copolymers obtained are according to Example 7 in the raw, unvulcanized and tested for their adhesive strength in the mixed, unvulcanized state. Table XIV shows the results.

- 56 -

609882/1187

Table XIV

Polymeric
station
attempt-
No. Bound
denes
Styrene,
Weight % M. Percentage service
micro structure vinyl Maximum
crystal
melting point
oc 110 9.4 4.24 trans 6.9 -4, 29.5 111 14.7 3.85 76.5 7.1 -6.5 S. 112 5.0 6.25 77.7 6.7 6.5, 32.1 113 13.7 3.10 79.2 7.4 -6.5 S. 114
I. nature
chews
schuk D 3.56 74.5 28 60988 UI Ni

Adhesive strength

seemingly

really

kp / cm (psi) kp / cm (psi) MPa

2.19 (31.2). T 1.98 (28.2) 0.19

1.86 (26.5) T 1.74 (24.7) 0.17

1.14 (16.2) T 1.14 (16.2) 0.11

1.71 (24.3) U 1.26 (17.9) 0.12

2.18 (31, O) U 1.82 (25.9) 0.18

Comments: Dj same as in example 6;

S: single melting endotherm " T: determined on the raw polymer;

U: Polymer first mixed with the following ingredients:

cn co ο cn cn co

Parts by weight component

100 polymer

20 HAF-HS carbon black

20 FEF carbon black

5 "Philrich" No. 5-Ö1, high-

aromatic oil, Phillips Chem. Co.

2 stearic acid 1 sulfur

3 zinc oxide

1 "Santocure"

2 "AgeRite Superflex", a diphenyl

amine-acetone reaction product, Antioxidant, R. T. Vanderbilt Co., Inc.

Example 18

A barium salt is prepared according to Example 1, Experiment 1, however, a molar ratio of water / tert-butanol of 5:95 applies. Then polymerized butadiene in toluene at 15 ° C by the general method of Example 2 using some other butyllithium compounds. The different polymerization conditions and the results are shown in Table XV.

609882/1 187

GT-871-F S3

Table XV

Poly-

meri-. MoI-

sa- um- ver Percentage maximum concentration type of wall- holds- butadiene crystal ver- butylli- butalation, nis micro structure smelting diene, % B ^ t ⁺ / Γη 1 point,

No. (mmol) g (hrs.) Li ⁺ *) trans vinyl ⁰ C

120 normal 24.8 97 0.52 80.4 6.8 5.90 32,

(0.72) (113, over

the where-. marriage end)

121 sec 21.5 100 0.53 ^; 78.7 6.2 7.39 34,

dar (41)

(0.71)

122 tertiary 24.2 100 0.52 80.0 6.5 6.09 32, (0.72) (41)

'see. the footnote in Table II

Example 19

The green strength (strength in the unvulcanized or uncured state) of a blended SBR copolyra according to the invention (high trans content) is compared with that of blended natural rubber. The SBR copolymer is the same as in Example 3, Experiment No. 20. The natural rubber (D) is the same as in Example 6. In each case 100 parts by weight of the polymer are mixed with 20 parts of HAF-HS carbon black, 20 parts of FEF carbon black, 3 parts of zinc oxide, 2 parts of stearic acid, 1.2 parts of "Age Rite Spar" (a mixture of mono-, di- and tri-styrene-substituted phenols, antioxidant, RT Vanderbilt Co., Inc.), 1.2 parts of "Santocure" and 2.25 parts "Crystex" (refined sulfur, approximately 90 % insoluble, Stauffer Chemical Co.). The mixed but unvulcanized or uncured rubber compounds are tested. Table XVI shows the results.

- 59 -

609882/1187

GT-871-F

Table XVI

Feed

speed on ■ '

Instron tester

Tensile strength in the "green" state, kp / cm2 (psi) MPa

Elongation at break, %

Natural rubber

SBR with a high trans content

2.54 cm / min 50.8 cm / min 2.54 cm / min 50.8 cm / min

26.72 (380) 2.62

792

52.38 (745) 5.14

832

29.46 (419) 2.89

1535

45.84

(6525 4.50

1821

SBR 1712, a butadiene / styrene copolymer with about 23.5 % styrene units produced by cold emulsion polymerization, shows a tensile strength in the "green" when mixed at the standard feed rate of 50.8 cm / min (20 in./min.) Condition of 3.47 kg / cm (49.3 psi) or 0.34 MPa; See "Rubber Age" (April 1974), p. 52.

- 60 -

609882/1187

Claims (1)

Claims Polymerization process, wherein a polymerizable vinyl monomer with an activated double bond and up to 14 carbon atoms, which is free of groups that would destroy the catalyst complex, under inert conditions in a hydrocarbon solvent at a temperature of about -90 to 100 ⁰ C in the presence of a Polymerized catalyst, which is a complex of. Ba 40-C-R) £ 0H), (^) where at least one of the radicals R is a methyl or cyclohexyl group and the remaining radicals R are the same or represent various alkyl or cycloalkyl radicals having 1 to 6 carbon atoms, and the molar ratio a / b is about 99.5: 0.5 to 88:12, and R ¹ Li (2) where R * is a normal, secondary or tertiary alkyl or cycloalkyl radical having 2 to 20 carbon atoms, the molar ratio (1) to '(2), based on barium metal and lithium metal, being about 0.30: 1 to 0.75: 1 and the solvent dissolves the monomers and polymers,
represents. -, 61 ~ 609882/1187 GT-871-F Polymerization process wherein (I) 1,3-butadiene or (II) a mixture of 1,3-butadiene with up to about 15% by weight (based on the total weight of the mixture) Styrene and / or isoprene under inert conditions in a lower-alkyl-substituted benzene as a hydrocarbon solvent polymerized at a temperature of about -20 to 40 ° C in the presence of a catalyst, which is a complex of wherein at least one of the radicals R is a methyl or cyclohexyl group, and the remaining radicals R are identical or different alkyl or cycloalkyl groups having 1 to 6 carbon atoms .., and the molar ratio a / b is about 99, 5: 0.5 to 88: 12 is, and R ¹ Li (2) where R * is a normal, secondary or tertiary alkyl or cycloalkyl radical having 2 to 20 carbon atoms, the molar ratio (1) to (2), based on barium metal and lithium metal, being about 0.35. : 1 to 0.60: 1 and the solvent dissolves the monomers and polymers,
represents. 3. The method according to claim 2, characterized in that the molar ratio of (1) to (2) is about 0.50: 1. 4. The method according to claim 2, characterized in that the quantitative ratio of the catalyst complex to the monomers about 0.00001 to 0.1 mol of catalyst complex (expressed as lithium metal) per 100 g of total monomer (s) amounts to. - 62 - 609882/1187 5. The method according to claim 4, characterized in that the quantitative ratio of the catalyst complex to the monomers about 0.00033 to 0.005 moles of the catalyst complex (expressed as lithium metal) per 100 g total - Monomer (s) is. 6. The method according to claim 2, characterized in that the radicals R are methyl groups and the radical R ^{1 is} a
Is an alkyl radical having 2 to 10 carbon atoms. 7. The method according to claim 2, characterized in that the a / b molar ratio is about 97.5: 2.5 to 90:10. · "-. 8. The method according to claim 7, characterized in that the temperature is about 0 to 30 ° C. 9. The method according to claim 8, characterized in that the solvent is toluene and R ^{1 represents} a butyl group. 10. The method according to claim 2, characterized in that the solvent at least not in a substantial way Extent acts as a chain terminator. 11. Compounds of the general formula below r / Ba where at least one of the radicals R is a methyl or cyclohexyl group and the remaining radicals R are the same
or are different and represent alkyl or cycloalkyl radicals with 1 to 6 carbon atoms and the MoI- - 63 - 609882/1 187 ratio a / b is about 99.5: 0.5 to 88: 12. 12. Compounds according to claim 11, characterized in that the molar ratio a / b is about 97.5: 2.5 to 90:10 amounts to. 13. Compounds according to claim 12, characterized in that the radicals R are methyl groups. 14. Process for the preparation of a compound represented by the following general formula JL Ba [40-C ~ R R where at least one of the radicals R is a methyl or cyclohexyl group and the remaining radicals R are the same or are different and represent alkyl or cycloalkyl radicals having 1 to 6 carbon atoms and the molar ratio a / b is about 99.5: 0.5 to 88:12, characterized in that one is in an inert atmosphere Barium metal in liquid ammonia or an amine solvent for the barium with a tertiary carbinol the general formula below HO-CR ^X R in which the radicals R have the meaning given above, and causes water to react, the molar ratio of carbinois to water being about 99.5: 0.5 to 88: 12, the temperature during the reaction in the range from about -100 ⁰ C to boiling point - 64 - 609882/1 187 of the solvent and the amine is a saturated, non-marriage-forming, non-polymerizable aliphatic, cycloaliphatic or heterocyclic, primary or secondary monoamine or polyamine (or a mixture of such amines) with 1 to 12 carbon atoms and 1 to 3 nitrogen atoms is used, and that after the reaction, the compound formed by the ammonia or amine solvent and separates any excess carbinol. 15. The method according to claim 14, characterized in that the molar ratio a / b is about 97 _t 5: 2.5 to 90:10. 16. Composition of substances for anionic polymerization in the form of a complex of where at least one of the radicals R is a methyl or cyclohexyl group and the remaining radicals R are the same or are different and each represent an alkyl or cycloalkyl radical having 1 to 6 carbon atoms and the molar ratio a / b is about 99 »5 J 0.5 to 88:12, and R'Li. (2) where R ^{1 is} normal, secondary or tertiary
Represents alkyl or cycloalkyl radical with 2 to 20 carbon atoms, where the molar ratio (1) to (2), based on barium metal and lithium metal, is about 0.30: 1 to 0.75: 1. - 65 -609882/1 187 17. The composition according to claim 16, characterized in that the molar ratio of (1) to (2), based on Barium metal and lithium metal, about 0.35: 1 to 0.60: 1. 18. Composition according to claim 16, characterized in that the molar ratio (1) to (2) is about 0.50: 1 amounts to. 19. The composition according to claim 16, characterized in that the radicals R are methyl groups and R ^{1 represents} an alkyl radical having 2 to 10 carbon atoms. 20. The composition of claim 16, characterized in that the molar ratio a / b is about 97.5: 2.5 to 90:10. 21. Composition according to claim 16, characterized in that R ^{1 is} a butyl group. 22. Rubber-like polymer in the form of 1,3-homopolybutadiene or a random copolymer of 1,3-butadiene with up to about 15% by weight (based on the total weight of the copolymer) styrene and / or isoprene units, which a) determined by differential thermal analysis freezing or glass transition temperature of about -80 to -100 ⁰ C. b) a crystal melting point (maximum values) determined by differential ^{thermal analysis l} dLm • unstretched state of approximately -10 to 43 ⁰ C, c) a trans-1,4 proportion of about 70 to 81 % and. a vinyl content of up to about 12 % for the butadiene units, - 66 - 609882/1 187 d) a heterogeneity index of about 4 to 40, e) an average molecular weight (number average) from about 20,000 to 300,000, f) Crystallinity after stretching or elongation in the unmixed and uncured or unvulcanized state due to the X-ray diffraction values, g) green strength and adhesiveness or stickiness (building tack) and h) one determined by gel permeation chromatography has broad molecular weight distribution. 23. Copolymer according to claim 22, characterized in that it contains styrene units as comonomer units. 24. Copolymer according to claim 22, characterized in that it contains isoprene units as comonomer units. 25. Copolymer according to claim 22, characterized in that that it contains isoprene and styrene units as comonomer units. - 67 - 609882/1187